CN1935392A - Method for the passivation of the surface of coated metal bands and device for the application of the passive layer on a metal coated steel band - Google Patents
Method for the passivation of the surface of coated metal bands and device for the application of the passive layer on a metal coated steel band Download PDFInfo
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- CN1935392A CN1935392A CNA2006101542830A CN200610154283A CN1935392A CN 1935392 A CN1935392 A CN 1935392A CN A2006101542830 A CNA2006101542830 A CN A2006101542830A CN 200610154283 A CN200610154283 A CN 200610154283A CN 1935392 A CN1935392 A CN 1935392A
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- pipe
- tin
- band
- aqueous solution
- steel band
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/76—Applying the liquid by spraying
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention provides a method for the passivation of the surface of metal bands covered with a coating, particularly tin-coated steel bands (S), which move at a band speed (v) through a coating installation. To allow an efficient passivation of the met al band surface even at high band speeds and simultaneously the lubrication of the coated metal band surface, after the coating process has been completed, an aqueous solution of a surface active substance is sprayed onto the coated metal band that moves at band speed (v). The invention further provides a device for the application of a metal coating on a steel band, particularly in a band tin-coating installation, as well as to the use of substances for lubrication and/or passivation during the manufacture of tin-coated steel bands, which can be sprayed as an aqueous solution on the tin-coated steel band.
Description
Technical field
The present invention relates to be covered with the surface passivation method of the metal tape (particularly covering the tin steel band) that is coated with application, it moves through coating unit with given belt speed; The invention still further relates to the equipment that in band tin-coating installation, is used on the steel band of washing, using passivation layer especially.In addition, the present invention relates to covering the application of tin steel band in making as the material of lubricated and/or passivator.
Background technology
In the manufacturing of covering tin plate (tinplate), particularly in band tin-coating installation with the electrolysis mode operation, make steel plate (the tin plate that the covers) passivation of coating with tin metal and chromium metal+chromium hydroxide (III) by chemical method or electrochemical process, degrease then, thereby the steel plate that makes coating is anti-oxidant and reduce coefficient of friction, thereby can more easily process the steel plate that applies in follow-up process.Usually use and contain Cr
6+Solution carry out passivation.In the prior art, for example in DE 4205819-A, DE 4403876-A, EP 0932453-A, EP 01002143-A, EP 01015662-A, WO99/67444-A, WO 00/46312-A and EP 01270764-A, also proposed not contain Cr
6+Passivating dip.These applications concentrate on the hot dipping that is used for auto industry mostly and electroplate the passivation that contains aluminium and surfaces containing zinc of thin plate and other hot dipping galvinized steel parts, and concentrate on the chromate-free passivation of covering tin plate on little degree.
Yet, when using metallizing to make food containers,, be different with their application in auto industry to the requirement of described material anti-oxidant and therefore aspect the passivation of metal surfaces.Passivation must prevent the undue growth of stannic oxide layer in the food containers storage process especially, and this undue growth can cause deposition (lacquering) or the consumption of the material that causes being saved.In addition, coating metal surfaces meeting not desirably variable color owing to catching corvinus or golden yellow, this can cause the rotten impression of internal material to the consumer.In addition, passivation must guarantee that canister can resist acid contained in the food after the food of packing into, for example sulfydryl-amino-carboxylate anion, for example cysteine and methionine.If passivation deficiency, this acid anion in the filling material can cause the delamination of internal tank lacquer.
In covering the common manufacturing of tin plate in band tin-coating installation, after covering tin and fusion, with the meticulousst metallic plate chilling in first water-bath, the water rinse and the heated drying of complete desalination are used in passivation in chromatedsolution then at last.Then, carrying out static with di-n-octyl sebacate (DOS) or acetyl tributyl citrate (ATBC) lubricates.By with tin surfaces=Sn=O and=the Sn-OH radical reaction, will cover the chromate reduction that adsorbs on the tin plate and become Cr
3+, under the situation of electrochemistry negative electrode passivation, also partly be reduced into the chromium metal.Cr
3+With Cr
3+The form precipitation of hydroxide.After covering tin plate surface rinsing and drying, passivation layer no longer contains Cr
6+
Consider foregoing, the method and apparatus that the purpose of this invention is to provide metal tape (particularly the covering the tin steel band) surface passivation that is used to make coated thing covering, this metal tape moves through coating unit with a belt speed, even this device also can be realized effective passivation of surfaces of metallic strip under high belt speed.In addition, be lubricated step simultaneously with the passivation of surfaces of metallic strip, thereby needn't carry out the coefficient of friction that extra subsequent processing steps reduces the metallizing belt surface.Purpose of the present invention also comprises the surface passivation that is provided for the metallizing band and/or lubricated product, and these products can be used for method of the present invention.
Summary of the invention
By the surfaces of metallic strip deactivation method, at the equipment of using the metal coat thing on the steel band with covering the material that is used as lubricated and/or passivator in the manufacturing of tin metal band, can realize these purposes.
According to the method that makes the surfaces of metallic strip passivation that is covered by the metal coat thing of the present invention, after tin deposits on the metal tape that moves through coating unit, spray the aqueous solution of surface reactive material.The preferred compression roller that uses is extruded and is evaporated to the aqueous solution of surface reactive material dried.The extruding and drying after, have only the film of surface reactive material to stay on the metallizing belt surface, wherein the overlay capacity of this film be generally the 2-15 milligram/square metre.Surface reactive material can be siloxanes, particularly polymethyl siloxane or the siloxanes that contains PEO.Perhaps, it can be copolymer, particularly acrylate copolymer.Preferably by pipe sprayed surface active material, these pipes have at interval with the metallizing belt surface and have perforation, and the aqueous solution arrives the metallizing belt surface by these perforation.Preferably each side at metal tape is equipped with at least one pipe that has these perforation, so as on two faces of metal tape equal sprayed surface active materials.
Material of the present invention has shown and has been especially suitable for use as surface reactive material.Use these materials, can obviously be reduced in the tin oxide growth on the metallizing belt surface.According to the present invention during with these mass treatment surfaces of metallic strip, the coefficient of friction of the surfaces of metallic strip of so handling is reduced to so low value simultaneously, thus can save after this with DOS carry out lubricated.The surfaces of metallic strip of handling according to the present invention has shown quite is of value to japanning.Material of the present invention is particularly suitable for method of the present invention because they under the situation of not adding organic solvent, have/comprise enough water-solublely, and therefore can be used as the aqueous solution and be sprayed onto on the surfaces of metallic strip.In addition, because their surface-active, these materials also can separate with the homogeneous film form on the surfaces of metallic strip with the very high belt speed above 500 meters/minute.
Brief description of drawings
With reference to the accompanying drawings, use object lesson and contrast test to explain the present invention in more detail.In the accompanying drawings:
Fig. 1 be can implement method of the present invention, be used to make the band tin-coating installation schematic diagram that covers tin plate; With
Fig. 2 is the perspective diagram of paralysis facility of the band tin-coating installation of Fig. 1.
The specific embodiment
The parts that the band tin-coating installation that tin plate uses is covered in the manufacturing that Fig. 1 shows in schematic form comprise application equipment, and application equipment does not show in the figure.In this application equipment, steel band S moves through and covers tin bath, and has been applied tin by electrolysis in this process.Before covering the tin process, the steel band S electrolysis that will be used for this is taken off lubricated, with the water rinse of complete desalination, carries out acidleach then and carries out rinse cycle with the water of complete desalination.The steel band S that so cleans is connected to negative electrode then, arrives the tin bath that covers that contains electrolyte and tin anode.Cover under the situation of tin bar spare in continuous monitoring and adjusting, on steel band, realized the densification of firm attachment, uniform tin precipitation with high current density.After electrolysis, tin surfaces is exposed under the fluid (flux), that is to say, it is wetting in 20-70 ℃ of solution of 1 grams per liter HCl or 3 grams per liter zinc chloride/ammonium chloride solutions, extrusion solution then, drying finally by inductance or by the of short duration fusion of resistance heated in the fusion tower, is covered the glossy surface of tin plate with manufacturing.
Then, will cover tin steel band S via deflection roll U guiding quench tank 1.In quench tank 1, the temperature of the water (FD water) of desalination is 70-95 ℃ fully.Then with coated steel strip S with common 200-600 rice/minute belt speed v via deflection roll U guiding by paralysis facility 2.Paralysis facility is illustrated among Fig. 2 in detail with the perspective view form.
Paralysis facility 2 comprises the vertical groove 5 that has downpipe 6.Near the bottom, in vertical groove 5 inside deflection roll U is installed, through its guiding coated steel strip S.On the top of vertical groove 5, be provided with pipe 11 in the both sides of steel tape S.Manage 11 parallel to each otherly, and vertically or at least be approximately perpendicular to the direction of feed (wherein in Fig. 2, direction of feed is to the top from the bottom) of band v.Provide several perforation 13 in 11 at pipe, they pipe vertically on partitioned arrangement mutually.These perforation 13 are relative with steel tape S.Pipe 11 is received in surface reactive material the aqueous solution from pump 14.Between pump 14 and tube inlet, on each pipe 11, through-flow meter 15 is installed.
On the direction of feed of band v,, two couples of compression roller 12a, 12b are set pipe 11 rears (just in Fig. 2, managing above in the of 11).On the band direction of feed, first couple of compression roller 12a and manage and be spaced apart about 20-100 centimetre between 11.Pipe 11 and the interval of coated steel strip S are generally 1-50 centimetre and be preferably 5-15 centimetre.Every pipe 11 has or comprises at least one perforation or perforate, yet preferably as shown in Figure 2, every pipe has/comprise a plurality of perforation in shell, they pipe vertically on apart from one another by arrangement.Every pipe 11 preferably has/comprises 5 perforation, and the diameter of perforation is the 1-4 millimeter, preferred 2-3 millimeter.Yet, also can use the pipe that a perforation or several perforation (for example reaching most 50 perforation) are only arranged.
Compression roller to 12a, 12b on the band direction of feed, be positioned at approximately 20-100 centimetre of roller 11 back, use them to squeeze and remove the solution that has been sprayed onto on the steel strip surface, thereby on steel strip surface, only stay the layer that has or comprise several molecular layers of the aqueous solution, and may only stay the monolayer of solution.
Excess solution, particularly be extruded the solution that roller 12 is extruded from coated steel strip S, be collected in the vertical groove 5, and flow into the storage tank 4 that is positioned at vertical groove 5 belows by downpipe 6, from this storage tank with the aqueous solution by pump 8 guiding recycling steps, transfer in the groove 9 at this solution that storage tank 4 is collected, surfactant concentration can be risen to desired value at this, and in the final pumping return pipe 11.
After passing through paralysis facility 2, coated steel strip S finally is transported in the drying equipment 10 via deflection roll U, and it comprises for example hot-air drier.
In above-mentioned paralysis facility 2, handle and cover the tin steel band with having variable concentrations and having or comprise the different different surfaces active materials of forming, and detect them with the non-oxidizability of measuring them and their coefficient of sliding friction.
Be adapted at the material that uses in the tin plate surface passivation method that covers of the present invention and must have/comprise surface-active, thereby they can be attached on the hydrophobic group on the tin surfaces, and simultaneously under their hydrophilic group effect, improve the wetability of the enamelled coating of in follow-up tin surfaces japanning process, using.Combining between the functional group on the functional group on the tin surfaces and the lacquer surface of containing bonding molecule must be very firm after drying varniss, so that they can be not destroyed (at 3.63 grams per liter KH in the cysteine test
2PO
4With 7.22 grams per liter Na
2HPO
42H
2Sterilized 90 minutes at the 121 ℃ of tin plates that cover that will paint in the solution of O and 1 grams per liter cysteine).In addition, used material should be dissolved in distilled water with the concentration up to 2 grams per liters under the situation of not adding organic solvent, because the use of solution reinforcing agent can cause the concentration of solvent in the waste gas too high, and therefore needs expensive cleaning device to remove solvent.Shown specially suitable material be preferably used as in practice additive with improve pigment in lacquer dispersiveness or improve the crosslinked and/or bonding material of lacquer on the metal surface.
Shown that following material is suitable especially:
A) have the polymer of the chemical composition of the polymethyl siloxane that has polyether lateral chain, its refractive index is 1.456-1.466 and is 1.09-1.13 gram/cubic centimetre 20 ℃ density,
B) have the polymer of the chemical composition of acid polyethers, its density is 1.20-1.30 gram/cubic centimetre, and acid index be 270-310 milligram KOH/g and
C) comprise the polymer of following ingredients:
I) monomer of one or more following formulas of 0-80 mole %:
R wherein
1, R
2, R
3And R
4Can be identical or different, and represent H or alkyl,
The ii) monomer of one or more following formulas of 0-70 mole %:
R wherein
5, R
6And R
7Can be identical or different, and represent H or alkyl, and R
8Represent alkyl or substituted alkyl, and alkyl R
8Can insert-the O group,
Iii) the following monomer of one or more of 5-50 mole %---it comprises the heterocyclic group with at least one alkaline theheterocyclic nitrogen atom, or this heterocyclic group is connected to after polymerization on this monomer,
The iv) following monomer of one or more of 0-10 mole %---it comprises and one or morely is reactive group for crosslinked or coupling,
V) one or more of 0-20 mole % do not belong to i)-the iv) monomer of group, i wherein) the group monomer is at least 20 moles of % with the amount that comprises the monomer of acrylate group, and organic salt.
In the method for the invention, these materials are sprayed onto with aqueous solution form cover on the tin steel band, optional then squeezing removed and dry.
Table 1 has been listed suitable in principle and has been used for the number of substances of the laboratory test of the inventive method, in laboratory test, ultra-fine lamella foil is covered tin, use the desalted water rinsing, and use moisture film with lacquer plate (lacquerplate) coating equipment, after this only cover stay on the tin plate surface overlay capacity be 5 grams/square metre film.The aqueous solution of material shown in the table 1 is poured on the concentration of 1 grams per liter covers on the tin plate sample, squeeze and remove, use the hot-air drying then.Carry out following check on the tin plate sample covering of having handled thus then:
Measure tin and tin oxide overlay capacity (the every square metre of tin oxide institute consumed current that wherein is used to reduce be expressed as coulomb/square metre) by the tin oxide coulometry,
Use three balls to follow the trail of test and carry out sliding friction mensuration,
With CV device (Leco company) be determined at cover on the tin plate surface spray, squeeze to remove and the carbon content of dry aqueous coating and
The tin plate sample of handling that covers was stored for 6 weeks under 40 ℃ and 80% relative humidity, and store the formation that tin oxide is measured in the back at this.
The result of this experimental series is presented in the table 1.
Will according to manufacturing of the present invention and carry out after-treatment cover tin plate with 5 gram/square metre can coating PPG 3907-301/A (lacquer A) or epoxy resin coating (lacquer B) japanning.Covering behind these japannings detected on the tin plate to measure the resistance in the disinfecting process, wherein uses the anti-sterilization of following substance-measuring:
3% acetate (100 ℃/30 minutes)
1% lactic acid+2%NaCl (121 ℃/30 minutes)
Phosphate buffer
*+ 0.5L/ cysteine (121 ℃/90 minutes)
Phosphate buffer
*+ 1.0L/ cysteine (121 ℃/90 minutes)
*Phosphate buffer: 3.56 grams per liter KH
2PO
4+ 7.22 grams per liter Na
2HPO
42H
2O, pH7
These result of the tests with the anti-sterilization of covering tin plate of two kinds of lacquers (A and B) japanning are presented in the table 2.
Subsequently with three balls follow the trail of test detect in contrast test, detect cover the tin plate sample, to measure them before handling and the coefficient of sliding friction afterwards according to the present invention.At this, the tin plate that covers of electrochemical passivation with 2.8 gram/square metre tin overlay capacities is measured the following coefficient of sliding friction:
Do not contain lubricant: μ=0.40
Contain 4 milligrams of/square metre di-n-octyl sebacates
(DOS is according to common process): μ=0.20
The coefficient of sliding friction of crossing with the mass treatment shown in the table 1 according to the present invention that covers the tin plate sample all is listed in the table 1, and in 0.17 to 0.46 scope.
Compare with the untreated tin plate that covers, the sliding friction that the tin plate sample partly has/comprise obvious reduction of covering according to the present invention's processing, wherein, in some material, the coefficient of sliding friction of surveying even be lower than and the corresponding amount of common process of carrying out covering tin plate with DOS.
Compare with the common static that covers the tin plate surface of the ester that adopts DOS and so on is lubricated, use the tin plate sample of having handled that covers not observe any tin dirt relevant with production according to the present invention.On the other hand, particularly using under the commonsense method situation of covering tin plate lubricated with DOS, observe the dust deposit that is caused by production usually, this is problematic, because this can only eliminate by suitable expensive treatment program in device.The reason that does not have dust in the method for the invention may be use or passivating process in the rinsing effect of the aqueous solution, and it is lip-deep well attached in the deflection roll of non-driving to cover tin plate in second annular column of band tin-coating installation.With lubricated the comparing of carrying out,, obviously do not produce the tin wearing and tearing owing in annular column, cover a small amount of slip of tin plate and deflection roll with the conventional matter of DOS and so on.
The tin plate that covers of the present invention is handled, and for example, in covering the tin plate storage process or before coating with lacquer, has further reduced the tin oxide growth thereon.The commerce of using the commonsense method manufacturing and carrying out after-treatment is covered tin plate and is had following tin oxide amount of application down after 6 weeks of storage in humidity-warm conditions (40 ℃ and 80% relative humidity):
Not passivation: 100C/m
2
Dipping passivation: 40C/m
2
Electrochemical passivation: 20C/m
2
On the contrary, the tin plate sample that covers that has carried out after-treatment according to the present invention has/is comprising the value shown in the table 1 after corresponding the storage.
Scan the result of contrast test, can draw following results: cover tin plate when surface when being used for passivation in the method for the invention, material shown in the claim 23 or material type cover in the coating of having carried out after-treatment according to the present invention and produce optimum aspect the non-oxidizability of tin plate and the sliding friction.Material " EFKA 3580 " (silicone surfactant that has polyethylene oxide chain), " EFKA4560 " (modification acrylate that has polyethylene oxide chain), " EFKA 8512 " and " EFKA3570 " (the partially fluorinated acrylate that has polyethylene oxide chain) are all producing optimum aspect two kinds of performances (the low coefficient of sliding friction and the growth of low tin oxide).
Table 1: be used for covering the Chrome-free product of handling behind the tin plate surface, cover the lip-deep coefficient of sliding friction of tin plate, product coating and tin oxide in the laboratory after the test processes in coating
| Numbering | Manufacturing enterprise's title | Product | Active material (according to manufacturer) | Active material (%) | The coefficient of sliding friction | CV400 ℃-amount *** (mg/m 2C) | Tin oxide C/m 2 | |
| At first | 6 weeks | |||||||
| 1 | EFKA | EFKA 7310 | Organically-modified siloxanes | ＞95 | 0.17 | 2.9 | 34 | 88 |
| 2 | EFKA | EFKA 7315 | Organically-modified siloxanes | ＞95 | 0.17 | 2.8 | 31 | 86 |
| 3 | EFKA | EFKA 4550 | Modified polyacrylate | 50 in Wasser | 0.18 | 3.2 | 31 | 63 |
| 4 | Tego | Glide 100 | Polyether silicone-copolymer | 100 | 0.18 | 3.0 | 39 | 77 |
| 5 | EFKA | EFKA 4580 | Polyacrylate-emulsion | 40 in Wasser | 0.19 | 3.8 | 36 | 101 |
| 6 | Tego | Wet 280 | Polyether silicone-copolymer | 100 | 0.19 | 3.8 | 31 | 68 |
| 7 | EFKA | EFKA 4560 | Modified polyacrylate | 40 in Wasser | 0.19 | 2.8 | 34 | 63 |
| 8 | EFKA | EFKA 6225 | Fatty acid modified polyester | 100 | 0.19 | 2.8 | 33 | 87 |
| 9 | Tego | Glide 450 | Polyether silicone-copolymer | 100 | 0.20 | 3.0 | 34 | 72 |
| 10 | EFKA | EFKA 3500 | The polymer that contains fluorocarbon | 50 in Wasser | 0.21 | 2.8 | 36 | 116 |
| 11 | EFKA | EFKA 3570 | The polyacrylate of fluorocarbon modification | 60 in Wasser | 0.21 | 2.6 | 30 | 60 |
| 12 | EFKA | EFKA 8512 | Polyether acid | 100 | 0.22 | 2.4 | 26 | 57 |
| 13 | Tego | Dispers 752W | Copolymer+pigmentaffin.Gr. | 50 | 0.22 | 2.4 | 35 | 96 |
| 14 | EFKA | EFKA 3580 | Solvent-free modified polyorganosiloxane | 100 | 0.23 | 2.4 | 29 | 69 |
| 15 | Tego | Dispers 750W | Polymer-modified+pigmentaffin.Gr. | 40 in Wasser | 0.23 | 2.6 | 35 | 73 |
| 16 | Dow Chem. | DOW Z 6030 | Metacrylatf.Silan | 98 | 0.24 | 3.8 | 35 | 63 |
| 17 | Tego | Glide 440 | Polyether silicone-copolymer | 100 | 0.25 | 3.0 | 38 | 78 |
| 18 | GE Silicones | A-1230 | The polyoxyalkylene alkoxy silane | keine Angabe | 0.25 | 4.0 | 28 | 67 |
| 19 | Dow Chem. | DOW Z 6137 | Homopolymers e.aminofunkt.Silans | 24 in Wasser | 0.26 | 2.9 | 30 | 47 |
| 20 | Dow Chem. | DOW Z 6040 | Epoxyfunkt.Silan | 98 | 0.27 | 2.5 | 26 | 66 |
| 21 | Wacker | HF 86 | Triacetyl ethoxy ethylene base silane | 100 | 0.30 | 3.2 | 29 | 62 |
| 22 | GE Silicones | VS-142 | Aminoalkyl silane .vorhydrolysiert | keine Angabe | 0.33 | 2.5 | 29 | 59 |
| 23 | Tego | Dispers 715W | Sodium Polyacrylate | 40 in Wasser | 0.34 | 2.8 | 30 | 68 |
| 24 | GE Silicones | A-187 | Glycidoxypropyltrime,hoxysilane | keine Angabe | 0.35 | 2.5 | 29 | 71 |
| 25 | Wacker | Addid 911 | (3-(2.3-glycidyl) propyl group) trimethoxy silane | 100 | 0.37 | 2.2 | 21 | 76 |
| 26 | GE Silicones | A-189 | The sulfydryl propyl trimethoxy silicane | keine Angabe | 0.39 | 2.8 | 24 | 51 |
| 27 | Wacker | Addid 900 | N(3-(trimethoxysilyl)propyl-ethylendian) | 100 | 0.41 | 3.2 | 28 | 50 |
| 28 | EFKA | EFKA 6220 | Fatty acid modified polymer | 100 | 0.43 | 3.4 | 34 | 64 |
| 29 | GE Silicones | A-1110 | Aminopropyl trimethoxysilane | keine Angabe | 0.43 | 2.3 | 30 | 81 |
| 30 | EFKA | EFKA 4540 | Modified polyacrylate ** | 50 in Wasser | 0.43 | 2.5 | 34 | 65 |
| 31 | EFKA | EFKA 3522 | Modified polyorganosiloxane emulsion .APE-frei | 35 in Wasser | 0.46 | 2.4 | 31 | 51 |
For contrasting: have the commerce that contains chromic passivation layer and cover tin plate, in manufacturing works, cover tin
| The dipping passivation *+4mg/m 2DOS ** | 0.2 | 4.4 | 15 | 20 |
| Electrochemical passivation *+4mg/m 2DOS ** | 0.2 | 4.8 | 30 | 40 |
*At 25 grams per liter Na
2Cr
2O
7In the solution
*The DOS=di-n-octyl sebacate
* *The CV-amount, the side of covering the tin plate sample after processing records
Table 2: the anti-sterilization of covering the tin plate sample after the chromium-free treatment
| Numbering | Manufacturing enterprise's title | Product | Lacquer adhesiveness in sterilizing test (crosscut adherence test) | |||||||
| Lacquer A (PPG 3907-301/A) | Lacquer B (competitor's product) | |||||||||
| 3% acetate | 1% lactic acid+2%NaCl | Cystein | 3% acetate | 1% lactic acid+2%NaCl | Cystein | |||||
| 0.5g/l | 1.0g/l | O.5g/l | 1.0g/l | |||||||
| 1 | EFKA | EFKA 7310 | + | + | + | + | + | + | + | - |
| 2 | EFKA | EFKA 7315 | + | + | + | + | + | + | - | - |
| 3 | EFKA | EFKA 4550 | + | + | + | + | + | + | + | + |
| 4 | Tego | Glide 100 | + | + | + | + | + | + | - | - |
| 5 | EFKA | EFKA 4580 | + | + | + | + | + | + | - | - |
| 6 | Tego | Wet 280 | + | + | + | + | + | + | - | - |
| 7 | EFKA | EFKA 4560 | + | + | + | + | + | + | - | - |
| 8 | EFKA | EFKA 6225 | + | + | + | + | + | + | - | - |
| 9 | Tego | Glide 450 | + | + | + | + | + | + | + | - |
| 10 | EFKA | EFKA 3500 | + | + | + | + | + | + | + | - |
| 11 | EFKA | EFKA 3570 | + | + | + | + | + | + | - | - |
| 12 | EFKA | EFKA 8512 | + | + | - | - | + | + | - | - |
| 13 | Tego | Dispers 752W | + | + | + | + | + | + | - | - |
| 14 | EFKA | EFKA 3580 | + | + | + | + | + | + | - | - |
| 15 | Tego | Dispers 750W | + | + | + | + | + | + | - | - |
| 16 | Dow Chem. | DOW Z 6030 | + | + | + | + | + | + | - | - |
| 17 | Tego | Glide 440 | + | + | + | + | + | + | - | - |
| 18 | GE Silicones | A-1230 | + | + | + | + | + | + | - | - |
| 19 | Dow Chem. | DOW Z 6137 | + | + | + | + | + | + | + | - |
| 20 | Dow Chem. | DOW Z 6040 | + | + | + | + | + | + | + | - |
| 21 | Wacker | HF 86 | + | + | - | - | + | + | - | - |
| 22 | GE Silicones | VS-142 | + | + | - | + | + | + | - | - |
| 23 | Tego | Dispers 715W | + | + | + | + | + | + | - | - |
| 24 | GE Silicones | A-187 | + | + | - | + | + | + | - | - |
| 25 | Wacker | Addid 911 | + | + | - | - | + | + | - | - |
| 26 | GE Silicones | A-189 | + | + | + | + | + | + | - | - |
| 27 | Wacker | Addid 900 | + | + | - | + | + | + | + | + |
| 28 | EFKA | EFKA 6220 | + | + | + | + | + | + | - | - |
| 29 | GE Silicones | A-1110 | + | + | + | + | + | + | - | - |
| 30 | EFKA | EFKA 4540 | + | + | + | + | + | + | + | - |
| 31 | EFKA | EFKA 3522 | + | + | - | + | + | + | - | - |
For contrasting: have the commerce that contains chromic passivation layer and cover tin plate, in manufacturing works, cover tin
| The dipping passivation *+4mg/m 2DOS ** | + | + | + | + | + | + | + | + |
| Electrochemical passivation *+4mg/m 2DOS ** | + | + | + | + | + | + | + | + |
*At 25 grams per liter Na
2Cr
2O
7In the solution
*The DOS=di-n-octyl sebacate
The lacquer adhesiveness is good :+, entsprechend Gt 0-Gt 2
The lacquer poor adhesion :-, entsprechend Gt 3-G 15
Claims (23)
1. be covered with the metal tape that is coated with application, particularly cover the surface passivation method of tin steel band, this metal tape moves through coating unit with a belt speed, the method is characterized in that, after coating procedure, the aqueous solution of sprayed surface active material on the metallizing band that moves with described belt speed.
2. according to the method for claim 1, it is characterized in that, use the aqueous solution of compression roller compressive surface active material afterwards.
3. according to the method for claim 2, it is characterized in that, after the compressive surface active material with metallizing band drying.
4. according to the method for claim 3, it is characterized in that, after the surface of compressive surface active material and dry metallizing, have the film of surface reactive material, its overlay capacity be the 2-10 milligram/square metre.
5. according to the method for claim 1, it is characterized in that described surface reactive material is a siloxanes, particularly polymethyl siloxane or comprise the siloxanes of PEO.
6. according to the method for claim 1, it is characterized in that described surface reactive material is a copolymer, particularly acrylate copolymer.
7. according to the method for claim 1, it is characterized in that the aqueous solution of described surface reactive material is by at least one pipe spraying, this pipe and coating metal surfaces have at interval, and comprise at least one perforation, the aqueous solution arrives coating surface or each coating surface of metal tape by this perforation.
8. according to the method for claim 7, it is characterized in that pipe or every pipe comprise that 1-50 diameter respectively is the perforation of 0.1-5 millimeter.
9. according to the method for claim 7, it is characterized in that at least one pipe that has perforation of each side outfit of metal tape, the aqueous solution is sprayed onto on the metallizing belt surface by pipe, the metallizing band is arranged in these perforation opposites of pipe.
10. according to the method for claim 7, it is characterized in that, pipe or every pipe horizontal positioned, and with spaced surface 1-50 centimetre of metallizing band.
11. the method according to claim 10 is characterized in that, pipe or every pipe and metallizing band spaced surface 5-15 centimetre.
12. the method according to claim 1 is characterized in that, the aqueous solution is sprayed onto on the surfaces of metallic strip with the form of liquid jet, and wherein liquid jet is with respect to normal+45 ° impact coated surfaces of metallic strip to-45 ° the angular range.
13. the method according to claim 12 is characterized in that, liquid jet with respect to normal+15 ° to-15 ° angular range and preferred vertical ground impact coated surfaces of metallic strip.
14. the method according to claim 1 is characterized in that, the aqueous solution is in vertical groove internal spray, and vertical troughed belt is useful on the downpipe of excess surface active agent solution, and surfactant solution is collected on the metallizing band in this groove.
15. the method according to claim 12 is characterized in that, liquid jet impacts one of two surfaces of metal tape near surfaces of metallic strip being applied the zone of compression roller.
16. the method according to claim 4 is characterized in that, makes the tin cover layer fusion before passivation on the metallizing band, and contains the quench tank of deionized water with cooling by at least one.
17. the method according to claim 1 is characterized in that, belt speed is higher than 100 meters/minute, and be preferably 300-600 rice/minute.
18. on steel band, use the equipment of metal coat thing, particularly band tin-coating installation, comprising:
Application equipment, be used for belt speed operation by the steel band of this application equipment on electrolysis use thin metal layer, particularly tin layer, and be used for the fusion apparatus that tin is tectal, have the material quench tank; With
Be used to make the paralysis facility of the metal level passivation of using,
It is characterized in that paralysis facility comprises at least one pipe, on shell, have a plurality of perforation, and pipe and coated steel have at interval, and the aqueous solution of surface reactive material is sprayed onto on the coated steel strip surface that moves through paralysis facility by pipe.
19. the equipment according to claim 18 is characterized in that, is equipped with pipe on each face of the steel band of operation by paralysis facility, so as on two faces of steel band the aqueous solution of sprayed surface active material.
20. the equipment according to claim 18 is characterized in that, paralysis facility comprises the vertical groove that has downpipe, collects excessive surfactant solution in this groove, and surfactant solution flows to the storage tank that is arranged in vertical groove below by downpipe then.
21. the equipment according to claim 18 is characterized in that, on the steel band direction of feed, after every pipe or these pipes, is equipped with the aqueous solution that at least one pair of compression roller is sprayed with extruding.
22. the equipment according to claim 18 is characterized in that, these perforation along pipe with the distance that is equal to each other be arranged in respect to the direction of feed of mobile steel band laterally, particularly on the vertical line.
23. use the method for material in covering tin steel band manufacture process, this method comprises:
The material that comprises one of following material is provided:
A) have the polymer of the chemical composition of the polymethyl siloxane that has polyether lateral chain, its refractive index is 1.456-1.466, and is 1.09-1.13 gram/cubic centimetre 20 ℃ density,
B) have the polymer of the chemical composition of acid polyethers, its density is 1.20-1.30 gram/cubic centimetre, and acid index be 270-310 milligram KOH/g and
C) comprise the polymer of following ingredients:
I) 0-80 mole %, the particularly monomer of one or more following formulas of 5-80 mole %:
R wherein
1, R
2, R
3And R
4Can be identical or different, and represent H or alkyl,
The ii) monomer of one or more following formulas of 0-70 mole %:
R wherein
5, R
6And R
7Can be identical or different, represent H or alkyl, and R
8Represent the alkyl of alkyl or replacement, and alkyl R
8Can insert-the O group,
Iii) the following monomer of one or more of 5-50 mole %---it comprises the heterocyclic group with at least one alkaline theheterocyclic nitrogen atom, or this heterocyclic group is connected to after polymerization on this monomer,
The iv) following monomer of one or more of 0-10 mole %---it comprises and one or morely is reactive group for crosslinked or coupling,
V) one or more of 0-20 mole % do not belong to i)-the iv) monomer of group, i wherein) the group monomer is at least 20 moles of % with the amount that comprises the monomer of acrylate group, and organic salt, and
In covering tin steel band manufacture process this material is sprayed onto with aqueous solution form and covers on the tin steel band, wherein this material plays the effect of lubricant and/or passivator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005045034.2 | 2005-09-21 | ||
| DE102005045034A DE102005045034A1 (en) | 2005-09-21 | 2005-09-21 | Method for passivating the surface of coated metal strips and device for applying the passive layer to a metal-coated steel strip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1935392A true CN1935392A (en) | 2007-03-28 |
| CN1935392B CN1935392B (en) | 2012-07-04 |
Family
ID=37496410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101542830A Expired - Fee Related CN1935392B (en) | 2005-09-21 | 2006-09-19 | Method for the passivation of the surface of coated metal bands and device for the application of the passive layer on a metal coated steel band |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20070065589A1 (en) |
| EP (1) | EP1767665A3 (en) |
| JP (1) | JP5362951B2 (en) |
| KR (1) | KR101216697B1 (en) |
| CN (1) | CN1935392B (en) |
| AU (1) | AU2006206063A1 (en) |
| BR (1) | BRPI0603941B1 (en) |
| CA (1) | CA2558562C (en) |
| DE (1) | DE102005045034A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2006206063A1 (en) | 2007-04-05 |
| KR101216697B1 (en) | 2013-01-09 |
| BRPI0603941B1 (en) | 2017-04-11 |
| JP5362951B2 (en) | 2013-12-11 |
| BRPI0603941A (en) | 2007-08-14 |
| CN1935392B (en) | 2012-07-04 |
| US20070065589A1 (en) | 2007-03-22 |
| KR20070033256A (en) | 2007-03-26 |
| EP1767665A2 (en) | 2007-03-28 |
| CA2558562C (en) | 2014-11-04 |
| EP1767665A3 (en) | 2008-07-16 |
| JP2007084934A (en) | 2007-04-05 |
| DE102005045034A1 (en) | 2007-03-29 |
| CA2558562A1 (en) | 2007-03-21 |
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